CN103521267A - N2-substituted-1,2,3-triazole ligand auxiliary Cu (I) catalysts and applications thereof - Google Patents
N2-substituted-1,2,3-triazole ligand auxiliary Cu (I) catalysts and applications thereof Download PDFInfo
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Abstract
The invention relates to N2-substituted-1,2,3-triazole ligand auxiliary Cu (I) catalysts and applications thereof in reaction of azides and terminal alkynes. The catalysts comprise N2-substituted-1,2,3-triazole ligands and Cu(I) salts, wherein the molar ratio of N2-substituted-1,2,3-triazole ligands to Cu(I) salts is 1:0.5-1:3. The catalysts are advantaged in that the middle nitrogen on the ring of the N2-substituted-1,2,3-triazole ligand has lower electron cloud density than the other two nitrogens, the middle nitrogen is substituted by a nitrogen heterocyclic ring, and the ligand utilizes triazole nitrogen atom with high electron cloud density and other heterocyclic ring nitrogen atom as a ligand effectively, the coordination capability with monovalent copper ions is enhanced, and monovalent copper ions is stabilized. The synthesis is simple and the properties are stable. In the catalysis of monovalent copper ions to a cycloaddition reaction of terminal alkynes and azides, the catalyst dosage is small, the reaction conditions are mild, the product yield is high and the substrate adaptability is strong.
Description
Technical field
The present invention relates to a class part, catalyst and application thereof, the concrete class N2 that relates to replaces the auxiliary Cu(I of 1,2,3-triazoles part) catalyst and the application in triazo-compound reacts with Terminal Acetylenes thereof.
Background technology
Early stage 1, synthesizing mainly based on 1 of organic azide and Terminal Acetylenes of 2,3-triazole, 3-dipole Huisgen cycloaddition reaction, but this reaction needed has activated group on triazo-compound or alkynyl, this reaction needed high temperature or high pressure simultaneously, and the reaction time is long, and reaction selectivity is not high, yield is low, therefore the application of 1,2,3-triazoles compound is very limited.In 2002, Sharpless and Meldal have reported that respectively Cu (I) can efficiently promote the Huisgen[3+2 of Terminal Acetylenes and triazo-compound] cycloaddition reaction, this discovery has promoted the development of the click chemistry (click chemistry) based on this reaction and has promoted 1,2, the extensive use of 3-triazole compounds, development along with the click chemistry of Terminal Acetylenes and triazo-compound, research and discovery are more efficient, clean, substrate universality is strong, and selective high catalyst system and catalyzing is subject to extensive concern and becomes the focus of research.This catalyst system and catalyzing is mainly divided into four kinds at present:
(1) reduction of Cu (II) salt produces Cu (I) and catalyzes and synthesizes 1,2,3-triazoles, i.e. CuSO
45H
2o, Cu (OAc)
2, CuSO
4deng all, can interact with copper metal or other reducing agent (sodium ascorbate) and produce Cu (I) compound, then play catalytic action; But its majority is the application in Aquo System, some water sensitivity groups but need to react in organic solvent, the post-reaction treatment process of this system is relatively complicated simultaneously, the strict system of ask for something (as biochemistry and drug research field) is used inconvenient.
(2) Cu (0) oxidation produces Cu (I) and catalyzes and synthesizes 1,2,3-triazoles, and metallic copper is at some oxidant (CuSO
4, FeCl
3) lower Cu (I) catalytic reaction that generates of existence; But with metallic copper, compare with other catalyst system and catalyzing need to be longer reaction time and larger amount, this just need to be improved copper metal catalyst system.
(3) Cu (I) salt catalyzes and synthesizes 1,2,3-triazoles, i.e. CuI, and CuBr, CuCl, CuCN, the mantoquitas such as CuOAc can be used to catalysis and can obtain good productive rate in certain dicyandiamide solution; But the easy disproportionation of Cu (I) salt or oxidized, and the reaction system of Cu (I) salt catalysis need utilize specific solvent even to need to add alkali, makes its application have certain limitation.
(4) the auxiliary Cu (I) of part catalyzes and synthesizes 1,2,3-triazoles, and the research of wherein finding and developing efficient part is of greatest concern.Part can not only promote the conversion of Cu (I) intermediate, and energy and the more stable compound of Cu (I) formation, plays the effect of stablizing Cu (I) and strengthening Cu (I) catalytic activity, thereby has greatly improved the efficiency of reaction.At present for the research of the part of Cu (I) catalysis mainly based on polyamines, the baroque parts such as amine that many 1,2,3-triazoles replace, are difficult for syntheticly, application aspect is subject to certain restrictions.
Therefore synthetic a kind of simple in structure, the novel 1,2,3-triazoles part of design can be assisted the Huisgen[3+2 of Cu (I) efficient catalytic triazo-compound and Terminal Acetylenes] cycloaddition reaction has important Research Significance.
Summary of the invention
Technical problem to be solved by this invention be for above-mentioned prior art, provide a kind of and be easy to synthesize, the N2 of novelty simple in structure replaces 1,2,3-triazole part, it can assist the Huisgen[3+2 of Cu (I) efficient catalytic triazo-compound and Terminal Acetylenes] cycloaddition reaction synthetic 1,2,3-triazole, N2 replaces 1 simultaneously, the compound that 2,3-triazole part and Cu (I) form also can be stablized Cu (I) and strengthen the catalysis triazo-compound of Cu (I) and the Huisgen[3+2 of Terminal Acetylenes] cycloaddition reaction activity.
The solution that problem adopts that the present invention solves above-mentioned proposition is: the catalyst auxiliary Cu(I of N2 replacement 1,2,3-triazoles part), include N2 and replace 1,2,3-triazoles part and Cu(I) salt, wherein N2 replaces 1,2,3-triazoles part and Cu(I) mol ratio of salt is 1:0.5～1:3.
Press such scheme, described Cu(I) salt is CuX, wherein X=Cl, Br, I, CN or SCN.
Press such scheme, described N2 replaces 1,2,3-triazoles part, and its general structure is as follows:
Wherein R or R ' they are H atom, alkyl or aryl, and described azacyclo-comprises pyridine, pyrimidine, quinoline or isoquinolin.
Press such scheme, described alkyl includes methyl, ethyl, propyl group, normal-butyl or benzyl.
Press such scheme, described aryl is phenyl or substituted-phenyl.
Above-mentioned azacyclo-structural formula is as follows:
Press such scheme, described N2 replaces the preparation method of 1,2,3-triazoles part, includes following steps: get NH-1,2,3-triazole, azacyclo-, CuCl, L-proline, K
2cO
3mix, take DMSO as solvent, under the condition of argon shield, heat 80～95 ℃, react 4～8h, after reacting completely, be extracted with ethyl acetate organic phase anhydrous Na
2sO
4dry, filtering and concentrating obtains thick product, through thin-layer silicon plastic column chromatography separating-purifying.
Reaction equation is as follows:
Wherein, X is Br or I.
Described N2 replaces the auxiliary Cu(I of 1,2,3-triazoles part) catalyst as the Huisgen[3+2 that promotes triazo-compound and Terminal Acetylenes] application of the catalyst of cycloaddition reaction.
Press such scheme, N2 replaces 1,2,3-triazoles part and Cu(I) consumption of salt is the 0.01%-5% of Terminal Acetylenes, in amount of substance.
Press such scheme, described Huisgen[3+2] cycloaddition reaction solvent for use is the mixing of any one or they in alcohols, water, nitrile and DMF.
Press such scheme, described triazo-compound comprises alkyl azide compound, aryl azide compound, TMSN
3or TsN
3, described Terminal Acetylenes is the Terminal Acetylenes that aryl replaces Terminal Acetylenes or alkyl Terminal Acetylenes and silica-based replacement.
The triazo-compound the present invention is directed to and the Huisgen[3+2 of Terminal Acetylenes] cycloaddition reaction, its reaction expression is as follows:
R
1for alkyl, substituted alkyl, aryl, substituted aryl, ester group, aldehyde radical, carbonyl etc., R
2for alkyl, substituted alkyl, aryl, substituted aryl, replace silica-based, sulfonic group etc.
The present invention compared with prior art has the following advantages: N2 replaces 1,2,3-triazole part is the heterocyclic compound of rich nitrogen, in the middle of its ring is upper, on upper two other nitrogen of electron cloud density ratio of N, cloud density is little, middle nitrogen is replaced by nitrogen heterocyclic ring, this part effectively utilizes the nitrogen-atoms of triazole atom that cloud density is large and other heterocycle as part, strengthened the coordination ability with univalent copper ion, univalent copper ion is played to stabilization, this part and other part are compared in addition, synthetic simple, stable in properties.In the cycloaddition reaction of univalent copper ion catalysis Terminal Acetylenes and triazo-compound, catalyst amount is little, and reaction condition is gentle, and product yield is high, substrate strong adaptability.
The specific embodiment
Below in conjunction with embodiment, the present invention will be further described, but can not be as limitation of the invention.
Embodiment 1
N2 replaces the synthetic of 1,2,3-triazoles ligand 1
In 250mL round-bottomed flask, add successively NH-1,2,3-triazole (14.5g; 100mmoL), adjacent bromopyridine (17.4g, 110mmmoL); stannous chloride (0.99g, 10mmoL), L-proline(2.3g; 20mmoL); potash (20.7g, 150mmoL), DMSO(180mL); argon shield, oil bath is heated 85～95 ℃ and is reacted completely for approximately 6 hours.After reaction finishes, be extracted with ethyl acetate organic phase anhydrous Na
2sO
4dry, filtering and concentrating obtains thick product through thin-layer silicon plastic column chromatography separating-purifying, obtains white solid, 13.5g, and yield is 61%.The structural characterization of this compound is as follows:
1h NMR (400MHz, CDCl
3) δ 8.57-8.67 (m, 1H), 8.09-8.19 (m, 2H), 7.84-7.99 (m, 3H), 7.37-7.50 (m, 3H), 7.35-7.29 (m, 1H).
Catalytic reaction
In 50mL round-bottomed flask, add successively phenylacetylene (1.02g, 10mmoL), Azide benzyl (1.47g, 11mmoL), N2 replaces 1,2,3-triazole ligand 1 (4.45mg, 0.02mmol), CuI(3.81mg, 0.02mmol), the absolute methanol (25mL) of take is reaction dissolvent, stirring at normal temperature approximately 30 minutes, filtering and concentrating reactant liquor, recrystallization can obtain 2.34g white solid, is product 1,2,3-triazole, yield is 99%.Sign to this 1,2,3-triazoles is as follows: m.p:125-127 ℃,
1h NMR (400MHz, CDCl
3) δ 7.79 (d, J=3.6Hz, 2H), 7.66 (s, 1H), 7.23-7.45 (m, 8H), 5.57 (s, 2H);
13c NMR (150MHz, DMSO) δ 148.1,134.6,130.4,129.0,128.7,128.1,128.0,125.6,123.9,119.5,54.1; HRMS (ESI): calcd. (M+H+) 236.1182, found236.1181.
Embodiment 2
N2 replaces the synthetic of 1,2,3-triazoles part 2
In 100mL round-bottomed flask, add successively NH-1,2,3-triazole (1.45g; 10mmoL), adjacent bromo pyrimi piperidine (1.75g, 11mmoL); stannous chloride (99mg, 1mmoL), L-proline(0.23g; 2mmoL), potash (2.07g, 15mmoL); DMSO(35mL); argon shield, oil bath is heated 85～95 ℃ and is reacted completely for approximately 8 hours, TLC monitoring reaction course.After reaction finishes, with ethyl acetate and NH
4cl solution extraction, organic phase anhydrous Na
2sO
4dry, filtering and concentrating obtains thick product through thin-layer silicon plastic column chromatography separating-purifying, obtains white solid, 1.23g, and yield is 55%.The structural characterization of this compound is as follows:
1h NMR (400MHz, CDCl
3) δ 8.81 (s, 1H), 8.52 (d, J=4.0Hz, 1H), 8.25 (d, J=8.0Hz, 1H), 7.85-8.00 (m, 2H), 7.44-7.50 (m, 2H), 7.31-7.41 (m, 2H).
Catalytic reaction
In 100mL round-bottomed flask, add successively phenylacetylene (2.04g, 20mmoL), Azide benzyl (2.93g, 22mmoL), N2 replaces 1,2,3-triazoles part 2(22.3mg, 0.1mmoL), CuI(7.6mg, 0.04mmol), the absolute methanol (35mL) of take is reaction dissolvent, stirring at normal temperature approximately 30 minutes, filtering and concentrating reactant liquor, recrystallization can obtain 4.66g white solid,, be 1,2,3-triazole, yield is 99%.
The N2 making with embodiment 1 replaces 1,2,3-triazole ligand 1 is assisted Cu(I) at different catalytic amounts and temperature the response situation of catalysis phenylacetylene and Azide benzyl as following table, (wherein solvent is methyl alcohol, and N2 replaces 1, the mol ratio of 2,3-triazole ligand 1 and CuI is 1:1):
| Sequence number | Catalyst (moL%) | Temperature [℃] | Reaction time | Yield (%) |
| 1 | 0.5 | 25 | 30min | 99 |
| 2 | 0.5 | 50 | 10min | 99 |
| 3 | 0.1 | 25 | 2h | 99 |
| 4 | 0.1 | 50 | 25min | 99 |
| 5 | 0.05 | 25 | 8h | 99 |
As can be seen from the above table, when the consumption of catalyst is 0.5%, the reaction rate of catalysis is very fast, and 25 ℃ little with the difference of 50 ℃, can reach 100% conversion at 30 minutes, obtains quantitative yield.When the amount of catalyst is 0.1%, under the condition of 50 ℃, also very fast promotion reacts completely, at 25 ℃, as long as extend the reaction time, also can obtain the effect of quantitative yield, even when 0.05% catalytic amount, only need to extend the reaction time also can obtain quantitative yield.Therefore, such compound has higher catalytic efficiency.
Embodiment 3
The N2 that makes with embodiment 1 replaces 1,2,3-triazoles ligand 1, investigates Cu(I) salt replaces with N2 the effect that 1,2,3-triazoles ligand 1 is pressed different amount ratio catalytic reactions, take and reacts as follows as example, the results are shown in following table.
In 50mL round-bottomed flask, add successively phenylacetylene (1.02g, 10mmoL), Azide benzyl (1.47g, 11mmoL), 1,2,3-triazoles ligand 1, its consumption of CuI(see the following form), the absolute methanol (25mL) of take is reaction dissolvent, stirring at normal temperature, processing method is all filtering and concentrating reactant liquors, recrystallization can obtain white solid 1,2,3-triazole product (yield sees the following form).
The response situation that the N2 that makes with embodiment 1 replaces 1,2,3-triazoles ligand 1 auxiliary CuI catalysis phenylacetylene and Azide benzyl at different catalytic amounts and temperature is as following table (wherein solvent is methyl alcohol):
As can be seen from the above table, N2 replaces the auxiliary Cu(I of 1,2,3-triazoles part) during salt catalytic reaction, N2 replaces the auxiliary and Cu(I of 1,2,3-triazoles part) salt different add ratio influential to the speed of reaction, but little on the yield impact of reaction.
Embodiment 4
The Terminal Acetylenes that the N2 replacement 1,2,3-triazoles part 2 auxiliary CuI catalysis that make with embodiment 2 contain special substituent (hydroxyl) reacts with organic azide.
In 1000mL round-bottomed flask, add successively phenylacetylene (28g, 0.5moL), Azide benzyl (73.23g, 0.55moL), 1,2,3-triazole part 2(0.19g, 1.0mmoL), CuI(0.48g, 2.5mmol), the absolute methanol (400mL) of take is reaction dissolvent, stirring at normal temperature approximately 30 minutes, filtering and concentrating reactant liquor, recrystallization can obtain white solid 93.6g, and yield is 99%.The structural characterization of this compound is as follows: m.p:69-71 ℃,
1h NMR (400MHz, CDCl
3) δ 7.46 (s, 1H), 7.31-7.38 (m, 3H), 7.23-7.27 (m, 2H), 5.45-5.51 (m, 2H), 4.69-4.75 (m, 2H);
13c NMR (100MHz, CDCl
3) δ 148.2,134.4,128.9,128.5,127.9,121.9,55.7,53.9; HRMS (ESI): calcd. (M+H+) 190.0975, found190.0974.
Claims (10)
1.N2 replaces the auxiliary Cu(I of 1,2,3-triazoles part) catalyst, include N2 and replace 1,2,3-triazoles part and Cu(I) salt, wherein N2 replaces 1,2,3-triazoles part and Cu(I) mol ratio of salt is 1:0.5～1:3.
2. by N2 claimed in claim 1, replace the auxiliary Cu(I of 1,2,3-triazoles part) catalyst, it is characterized in that described Cu(I) salt is CuX, wherein X=Cl, Br, I, CN or SCN.
3. by the 1,2,3-triazoles part/Cu(I described in claim 1 or 2) salt composite catalyst, it is characterized in that described N2 replaces 1,2,3-triazoles part, its general structure is as follows:
Wherein R or R ' they are H atom, alkyl or aryl, and described azacyclo-comprises pyridine, pyrimidine, quinoline or isoquinolin.
4. by N2 claimed in claim 3, replace the auxiliary Cu(I of 1,2,3-triazoles part) catalyst, it is characterized in that described alkyl includes methyl, ethyl, propyl group, normal-butyl or benzyl.
5. by N2 claimed in claim 3, replace the auxiliary Cu(I of 1,2,3-triazoles part) catalyst, it is characterized in that described aryl is phenyl or substituted-phenyl.
6. by N2 claimed in claim 3, replace the auxiliary Cu(I of 1,2,3-triazoles part) catalyst, it is characterized in that described N2 replaces the preparation method of 1,2,3-triazoles part, include following steps: get NH-1,2,3-triazole, azacyclo-, CuCl, L-proline, K
2cO
3mix, take DMSO as solvent, under the condition of argon shield, heat 80～95 ℃, react 4～8h, after reacting completely, be extracted with ethyl acetate organic phase anhydrous Na
2sO
4dry, filtering and concentrating obtains thick product, through thin-layer silicon plastic column chromatography separating-purifying.
7. N2 claimed in claim 1 replaces the auxiliary Cu(I of 1,2,3-triazoles part) catalyst as the Huisgen[3+2 that promotes triazo-compound and Terminal Acetylenes] application of the catalyst of cycloaddition reaction.
8. by application claimed in claim 7, it is characterized in that N2 replaces 1,2,3-triazoles part and Cu(I) consumption of salt is the 0.01%-5% of Terminal Acetylenes, in amount of substance.
9. by application claimed in claim 7, it is characterized in that described Huisgen[3+2] cycloaddition reaction solvent for use is the mixing of any one or they in alcohols, water, nitrile and DMF.
10. by application claimed in claim 7, it is characterized in that described triazo-compound comprises alkyl azide compound, aryl azide compound, TMSN
3or TsN
3, described Terminal Acetylenes is the Terminal Acetylenes that aryl replaces Terminal Acetylenes or alkyl Terminal Acetylenes and silica-based replacement.
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| CN105085553A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | O-phenanthroline hydrate bridged multi-core copper nitrogen heterocyclic carbene compound |
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| CN103880762A (en) * | 2014-04-08 | 2014-06-25 | 河南师范大学 | Preparation method of 1,2,3-triazole compound |
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| CN104001553A (en) * | 2014-06-20 | 2014-08-27 | 武汉工程大学 | N-substituted 1,2,3-triazole derivative/Cu(I) composite catalyst and synthesis and application thereof |
| CN104016968A (en) * | 2014-06-20 | 2014-09-03 | 武汉工程大学 | N1 substituted 1,2,3-triazole derivative for ligand of Cu(I) as well as preparation method and application of N1 substituted 1,2,3-triazole derivative |
| CN104016969A (en) * | 2014-06-20 | 2014-09-03 | 武汉工程大学 | N2-substituted 1,2,3-triazole derivative for Cu (I) ligand as well as preparation method and application of N2-substituted 1,2,3-triazole derivative |
| CN104001553B (en) * | 2014-06-20 | 2016-02-24 | 武汉工程大学 | 1,2,3-triazoles derivative/Cu (I) composite catalyst that N replaces and Synthesis and application thereof |
| CN110563659A (en) * | 2019-08-30 | 2019-12-13 | 浙江工业大学 | Method for preparing 1,2, 3-triazole compound by heterogeneous copper catalysis in one pot |
| CN113797965A (en) * | 2020-06-17 | 2021-12-17 | 中国科学院大连化学物理研究所 | Preparation method of titanium silicalite molecular sieve crystal-loaded copper nanoparticle catalyst |
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